Disordered Rocksalts with Lattice Oxygen Activation as Efficient Oxygen Evolution Electrocatalysts

Abstract

The lattice oxygen oxidation mechanism (LOM) provides an efficient pathway for accelerating the oxygen evolution reaction (OER) in certain electrocatalysts by activating and involving lattice oxygen in the catalytic OER process. We investigated the potential of disordered rocksalts as catalysts for accelerating the OER through the LOM process, leveraging their unique metastable Li–O–Li bond states. Theoretical calculations were employed to predict the catalytic pathways and activities of disordered rocksalts (DRX), such as Li_1.2Co_0.4Ti_0.5O₂ (LCTO). The results revealed that benefiting from the unhybridized Li–O electronic orbitals and the resulting metastable states of Li–O–Li bonds in DRX, LCTO exhibited a typical LOM pathway, and the lattice oxygen was easily activated and participated in the OER. The experimental results showed that LCTO exhibited a remarkable pH-dependent OER activity through the LOM pathway, with an overpotential of 241 mV at a current density of 10 mA/cm², and excellent long-term stability. This work provides a novel chemical space for designing highly active and stable OER electrocatalysts by leveraging the LOM reaction pathway.

Keywords

Lattice oxygen oxidation / Disordered rocksalts / Oxygen evolution reaction / Electrocatalysts

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